Structural and Physicochemical Properties of a Polymerizable Surfactant Synthesized from N-Methylol Acrylamide

Article abstract of DOI:10.1007/s11743-015-1785-4

A new polymerizable nonionic surfactant with reactive vinyl groups has been synthesized from N-methylol acrylamide using a two-step procedure. The structure of the surfactant molecule was characterized by Fourier transform infrared, ¹H nuclear magnetic resonance and mass spectroscopy. The surface active properties alongside its self-assembly properties were investigated by surface tension, electrical conductivity, and fluorescence spectroscopy measurements. As compared with other nonionic surfactants, this study showed that this polymerizable surfactant possesses slightly a higher critical micelle concentration (CMC) value and the surface tension value at CMC. The obtained CMC values were compatible among measurements, ca. 0.02-0.038 M. The evidence of micelle formation also provided by the zeta potential measurements and the obtained zeta potential values showed that the polymerizable surfactant solutions had limited stability. The hydrolysis stability and solubility of the polymerizable surfactant were also investigated. The solubility results have shown that it was soluble in polar solvents while insoluble in nonpolar solvents both at room temperature and 40 °C. The acidic and basic hydrolysis of the surfactant increased as the temperature increased and the hydrolysis stability was 180 min (basic medium) and 55 min (acidic medium) at 80 °C.

Full text of DOI:10.1007/s11743-015-1785-4

J Surfact Deterg
DOI 10.1007/s11743-015-1785-4
ORIGINAL ARTICLE
Structural and Physicochemical Properties of a Polymerizable
Surfactant Synthesized from N-Methylol Acrylamide
1
2
1
Yasemin Tamer
•
Hale Berber Yamak
•
H u¨ seyin Yıldırım
Received: 17 September 2015 / Accepted: 21 December 2015
Ó AOCS 2016
Abstract A new polymerizable nonionic surfactant with
reactive vinyl groups has been synthesized from N-
methylol acrylamide using a two-step procedure. The
structure of the surfactant molecule was characterized by
Keywords Polymerizable nonionic surfactant Á N-
methylol acrylamide Á Critical micelle concentration
(CMC) Á Physicochemical properties Á Surface tension
1
Fourier transform infrared, H nuclear magnetic resonance
and mass spectroscopy. The surface active properties
alongside its self-assembly properties were investigated by
surface tension, electrical conductivity, and fluorescence
spectroscopy measurements. As compared with other
nonionic surfactants, this study showed that this polymer-
izable surfactant possesses slightly a higher critical micelle
concentration (CMC) value and the surface tension value at
CMC. The obtained CMC values were compatible among
measurements, ca. 0.02–0.038 M. The evidence of micelle
formation also provided by the zeta potential measure-
ments and the obtained zeta potential values showed that
the polymerizable surfactant solutions had limited stability.
The hydrolysis stability and solubility of the polymerizable
surfactant were also investigated. The solubility results
have shown that it was soluble in polar solvents while
insoluble in nonpolar solvents both at room temperature
and 40 °C. The acidic and basic hydrolysis of the surfactant
increased as the temperature increased and the hydrolysis
stability was 180 min (basic medium) and 55 min (acidic
medium) at 80 °C.
Introduction
Surfactants, consisting of a hydrophilic head and a
hydrophobic tail unit in their molecules, play an essential
and versatile role in obtaining stable latexes with desired
properties in free-radical emulsion polymerization [1–3]. In
many applications lower molecular weight surfactants are
used, and they are adsorbed on particle surface with weak
H or r bonding interactions during the polymerization in
order to control both the size of the particles and the sta-
bility of the latexes [4, 5]. However, these physically bound
surfactants tend to migrate from the particle surface during
polymerization and film formation process and create a
separate phase. This causes some problems with latex and
film properties such as the lack of stability, water sensi-
tivity, high ionic strength, or lack of gloss and adhesivity
[6–10]. Those effects are major disadvantages of emulsion
applications like paints, adhesives, and other protective
coatings. In order to overcome these difficulties, poly-
merizable surfactants, which have a further reactive group
compared to conventional surfactants, can be used due to
their ability to undergo polymerization. Since polymeriz-
able surfactants are covalently incorporated into the poly-
mer chains by copolymerizing with the main monomers,
they connect to the particle surface and reduce the surface
tension effectively, thereby improving latex properties like
particle size, colloidal stability, etc. [11–13]. The use of
polymerizable surfactants in emulsion polymerization has
drawn much attention since the first discovery of them in
1958 [14]. Chen et al. reported that when a surfmer is used,
&
Hale Berber Yamak
haleberber@yahoo.com; hberber@yildiz.edu.tr
1
2
Department of Polymer Engineering, Yalova University,
7
7100 Yalova, Turkey
Department of Metallurgical and Materials Engineering,
Yıldız Technical University, 34220 Istanbul, Turkey
1
23

J Surfact Deterg
the surfactant migration is reduced and the water resistance
and surface adhesion are improved [15].
such as zeta potential, hydrolysis stability, and solubility
were performed to verify the micelle formation and their
charge properties.
Typical reactive groups such as vinyl, allyl, or acrylic
groups are located at the hydrophobic tail or hydrophilic
head group of the surfactant molecule [16]. To obtain novel
latex properties distinct from conventional surfactants,
different types of polymerizable surfactants, cationic,
anionic, and nonionic have been synthesized [5, 17, 18].
Among them, the nonionic ones bearing different reactive
parts (i.e., methacrylic, allylic, maleic, and vinylic) show
excellent surface activity and are not easily affected by
change of pH values [19].
Experimental
Materials
Acrylamide, formaldehyde, 4-methoxyphenol, sodium
hydroxide (NaOH), hydrochloric acid (HCl), sulfuric acid
(H SO ), pyrene, acetone, ethyl acetate, hexane, diethyl
2
4
N-methylol acrylamide (NMA) is a water-soluble
bifunctional nonionic monomer with polymerizable vinyl
and cross-linkable methylol groups. The condensation
reactions occur between its functional groups, and a vinyl
group bearing polymerizable surfactant is obtained. The
free vinyl groups retain a pendant from the polymer chain
and later undergo crosslinking reactions with groups of
other polymers or monomers [20, 21]. Because of these
important properties, thermoplastic polymers can be
formed by copolymerization of N-methylol acrylamide
with a variety of vinyl monomers by emulsion polymer-
ization, and they are widely used in industrial applications
such as coatings, textile, latex paints, adhesives, and bin-
ders [22, 23]. The use of small amounts of NMA in
emulsion polymerization may enhance the durability of
latexes and may give films with increased wrinkle resis-
tance, impact resistance, abrasion resistance, tensile
strength, peel strength, water, alkali, and solvent resistance
and gloss [24]. In the former studies, NMA was used as a
comonomer in emulsion polymerization of vinyl acetate
and several other monomers. It provided superior proper-
ties to the latexes such as colloidal stability, adhesion,
polarity, and improved the mechanical properties of the
films [25, 26]. In our previous study, NMA was used as a
cosurfactant in semi-batch emulsion polymerization of
vinyl acetate and butyl acrylate with different anionic and
nonionic emulsifiers. It was able to cause high conversion
of the monomer in small polymer particles, and the
obtained latexes were quite stable during and after the
polymerization process [20].
ether, methanol, ethanol, and chloroform were obtained
from Merck. All chemicals were reagent grade quality and
used without further purification. Deionized water was
used in all studies.
Synthesis of Polymerizable N-Methylol Acrylamide
(p-NMA)
NMA gives condensation reactions between its own func-
tional groups, and by using this property, an oligomeric
polymerizable surfactant was obtained. In a typical
experiment, 4-methoxyphenol (0.02 g) was mixed with
30 mL water and was heated to 60 °C, and then 42 g
acrylamide was added. After the solution was cooled to
room temperature, a 25 g formaldehyde solution was
added. The pH value of the solution was set to 10.5 by
adding 2.5 M sodium hydroxide (NaOH), and the solution
was stirred for 1 h. The temperature spontaneously
increased to 35–40 °C while preparing this solution. N-
methylol acrylamide and N,N-dimethylol acrylamide were
formed from the methylol reactions between acrylamide
and formaldehyde (Fig. 1). 4-Methoxyphenol was added to
the reaction medium to prevent the polymerization of
acrylamide with vinyl groups and allow the reactions
between the NH group of acrylamide and the carbonyl
2
The purpose of this study was to synthesize a new sur-
factant that can contribute to the increase in stability of the
emulsion polymerizations and the final latexes, and also to
the improvement of the latex and film properties of the
emulsion polymers. Polymerizable nonionic surfactant N-
methylol acrylamide (p-NMA) containing a reactive vinyl
group was prepared by condensation reactions. In this
study, we focused on characterizing the p-NMA structure
and investigating the physicochemical properties by the
surface tension method, electrical conductivity, and fluo-
rescence spectroscopy. In addition, other measurements
Fig. 1 Structure of p-NMA
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J Surfact Deterg
group of formaldehyde. In the second step, the pH value
was adjusted to 5.5 with 2.5 M sulfuric acid (H SO ) and
373 nm excitation wavelength. The intensity ratio (I /I ) of
1 3
the first (I ) over the third (I ) vibronic band of the emis-
1
2
4
3
0
.11 g 4-methoxyphenol was added into the reaction
sion spectrum of pyrene, was used to detect the micropo-
larity of hydrophobic microdomains [27, 28]. A series of
surfactant solutions with the same pyrene concentration
medium, and the final solution was stirred for 1 h. Con-
densation reactions occurred both between the functional
groups of NMA and N,N-dimethylol acrylamide. Poly-
merizable N-methylol acrylamide (p-NMA) was obtained
in 48 % aqueous solution.
-
7
(1.0 9 10 M) was prepared, and the solutions were
stirred at room temperature overnight to reach the equi-
librium of pyrene in the aqueous phase. The zeta potential
of p-NMA was measured with a Brookhaven 90 Plus/BI-
MAS on Zeta PLUS mode. All measurements were taken at
25 °C.
Characterization of Polymerizable N-Methylol
Acrylamide (p-NMA)
The solubility of p-NMA in different solvents was
estimated by placing 50 mg surfactant and 1 mL solvent.
The dissolution property was determined visually both at
room temperature and 40 °C. For hydrolysis stability, a
mixture of 10 mmoL polymerizable surfactant and 10 mL
0.1 N NaOH and 0.1 N HCl were separately placed in a
water bath at 40 and 80 °C, and the time required for the
solutions to be clouded was measured.
The surfactant structure was confirmed by recording FTIR
spectra with a Perkin Elmer Spectrum One FTIR (ATR
1
sampling accessory) spectrophotometer. H NMR spectra
were taken using a Bruker AV 400 MHz spectrometer in
DMSO. Mass spectrum was obtained by a MALDI-TOF-
MS system equipped with a 337 nm nitrogen UV-Laser
from Bruker Daltonics 67 Microflex (Germany) without
using a matrix.
The surface tension measurements were performed with
a tensiometer (KSV instruments, Sigma 701 model) using
the Wilhelmy plate method. The plate was carefully flamed
before measurement. The surfactant solutions prepared
with distilled water and the instrument were checked by
measuring the surface tension of distilled water. Five
readings were taken for each measurement to assure their
reproducibility. The conductivity measurements of surfac-
tant solutions were taken using a Eutech/Oakton PC 510
model conductometer, and the average of three measure-
ments was taken. The fluorescence spectrum was recorded
on a Jobin Yvon-Horiba Fluoromax-P fluorescence spec-
trophotometer at 25 °C using pyrene as a probe. The
emission spectra were scanned from 300 to 350 nm using a
Results and Discussion
Spectral Analysis of the Polymerizable Surfactant
P-NMA was synthesized in two steps, and it was obtained
as a 48.0 % wt aqueous solution. The water in aqueous
p-NMA solution was partially evaporated and dried under
vacuum at 60 °C and white crystals were obtained. This
crystal form was structurally characterized using IR-spec-
1
troscopy, H NMR and MALDITOF-MS techniques.
In the FTIR–ATR spectra (Fig. 2) of p-NMA, charac-
-
teristic peaks were observed. IR (cm ): 3306 (N–H
stretch), 3066, 2956 (C–H stretch), 1655 (C=O stretch),
1
Fig. 2 FTIR spectra of p-NMA
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J Surfact Deterg
1
Fig. 3 H NMR spectra of
p-NMA
The low intensity peak at m/z = 573.3 was obtained by
fragmentation of one repeating unit and a CH group from
2
the molecular ion peak. The peak at m/z = 544.9 having a
?
spacing of 28 reflected the C H unit. Elimination of an
2
4
?
CO molecule resulted in a molecular weight difference of
8 mass units and the most intense peak in the spectrum
2
called the base peak was obtained (m/z = 516.8). The
analysis results confirmed that the polymerizable surfac-
tant, p-NMA was synthesized as shown in Fig. 1. This
structure is composed of four repeating units and H– and
HO– groups are located at the end of the molecule and the
molecular weight was determined to be 802 g/mol.
Determination of CMC
Fig. 4 MALDITOF-MS spectra of p-NMA
Like other conventional low molecular weight surfactants,
polymerizable surfactants also form micelles above a cer-
tain concentration called the critic micelle concentration
(CMC). The CMC of surfactants can be determined by
measuring some physicochemical properties of their
aqueous solutions such as conductivity, surface tension,
and viscosity, and by using different methods such as light
scattering, calorimetry, fluorescence spectroscopy, and
nuclear magnetic resonance (NMR) spectroscopy as a
function of surfactant concentrations [29, 30].
1
300–1450 (C–H bend), 1223 (C–O stretch). The H NMR
1
spectrum of p-NMA was as follows: (DMSO, 400 MHz):
d = 6.10–6.20 (m, 8H, CH ), 5.50–5.60 (m, 8H, CH ),
2
2
6
.18–6.31 (m, 8H, CH), 8.11 (s, 1H, NH), 4.40–4.61 (m,
4
H, NCH OCH N), 4.55 (m, 2H, NCH O), 3.65 (t, 1H,
2
2
2
OH).The other peaks are due to the unreacted monomers
and residual substances (Fig. 3).
In the stick diagram (Fig. 4) showing the mass spectrum
of p-NMA, the peaks were separated by 196 mass units,
corresponding to the molecular weight of the repeating
unit. The line produced by the heaviest ion passing through
the machine at m/z = 782.8 is due to the molecular ion
Surface Tension
The obtained surface tension values of surfactant solutions
were plotted against the logarithm of the solution concen-
tration, and the resulting curve showed two distinct parts.
First, the surface tension of aqueous solutions of the sur-
factant decreased rapidly with addition of surfactant, and
then stayed constant. The CMC was determined from the
?
peak (M ). By analyzing this peak, the average degree of
polymerization (DP ) was calculated to be 4. Fragmenta-
n
tion of C–C bonds occurs because they are usually weaker
than C–H bonds, and this produces a mixture of vinyl,
methylene, carbonyl, nitrogen groups, and NMA monomer.
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J Surfact Deterg
Fig. 6 Variation in the electrical conductivity with p-NMA
concentration
Fig. 5 Surface tension versus log c, for nonionic p-NMA at 25 °C
breakpoint or slope change between two regions of the
curve (Fig. 5). At lower surfactant concentrations, surfac-
tant molecules were adsorbed at the air/water interface
until the solution surface was completely filled. The excess
amount of molecules created micelles and the surface
tension became constant at higher concentrations [5, 30].
The polymerizable nonionic surfactant prepared in this
study has an amphipathic structure different from tradi-
tional surfactants that usually have a distinct hydrophobic
tail. The CMC value of this surfactant depends on both the
hydrophobic and hydrophilic parts of the molecule. The
CMC decreases and micelle formation becomes easier with
increasing length of the hydrophobic moiety [30]. The
polymerizable C=C double bond remains on a phase sur-
face or even in water phase during the formation of
micelles. All of them influence the total surface activity of
the polymerizable surfactant [19, 29].
electrical conductivity values against increasing surfactant
concentration and the break point of two straight lines gave
the CMC value of p-NMA. Below CMC value, the con-
ductivity value rose with an increase in surfactant con-
centration due to the free surfactant ions in the medium.
The surfactant molecules formed micelles when the sur-
factant concentrations came to the intersection point. The
micelle mobility was lower than the free surfactant ions;
therefore, the conductivity increase was smaller at the
concentrations above the CMC [33].
The conductance data of p-NMA clearly showed a
broader inflection in the curve. The CMC value of the
surfactant was approximated as 0.025 M, and this was very
close to the value obtained from the surface tension
measurements.
Fluorescence Measurements
Due to the short-chain alkyl groups and presence of
extra hydroxyl and amino groups, the p-NMA may be able
to interact more strongly with water molecules, via
H-bonding, and micelle formation occurs at higher con-
centrations. The CMC value was 0.02 M, and the surface
To confirm the CMC value of p-NMA, fluorescence mea-
surements were carried out. Pyrene is the most commonly
used fluorescence probe and the characteristics of its
emission spectrum could be used to predict the polarity of
its environment [34, 35]. Before occurrence of micelles, the
pyrene molecule is situated in aqueous phase, but it is
located in a highly hydrophobic micelle core above CMC.
This polarity change in the environment reflects the spec-
tral characteristics of pyrene and the intensity ratio of the
first peak (*373 nm) to the third peak (*384 nm) (I /I )
-
1
tension value at the CMC was 44 mN m that indicated
the extent of interaction between water and p-NMA
molecules at the interface. As expected, short hydrophobic
chain length led to an increase of the CMC value, which
means that the hydrophobic domain was the predominant
driving force for micellization in aqueous solution [31].
Also, the lower surface tension value at the CMC indicated
rather good surface activity [32].
3
1
in the steady state emission spectra shifts while the envi-
ronment of pyrene changes. When the I /I intensity ratio is
3
1
plotted versus surfactant concentration, the CMC value can
be obtained from the midpoint of the plot [33, 36]. As
shown in Fig. 7, the constant I /I ratio began to fall by an
Conductivity
3
1
Conductivity is an easy method for determining the
micellar properties of surfactants [32]. Figure 6 shows the
increase in concentration to reach equilibrium, then
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Fig. 8 Zeta potential values versus different p-NMA concentrations
Fig. 7 Fluorescence measurements of pyrene solubilized in p-NMA
the CMC values obtained from other measurements. These
results showed that the solution became stable and higher
zeta potential values were obtained when the micelles
formed. As seen from Fig. 8, the zeta potential results were
obtained in negative values for all concentrations. These
negative values supported that the p-NMA molecules
formed micelles with the hydrophobic tail groups towards
the inside and the hydrophilic head groups (–OH) towards
the outside. It can be said that the end groups on the outer
surface of p-NMA and hydroxyl ions released by the dis-
sociation–association equilibrium of the water molecules
contributes to give a negative charge.
surfactant molecules formed micelles by surrounding the
pyrene, and the intensity ratio became constant. The CMC
value of the surfactant was approximated as 0.038 M, and
this value was slightly higher than those obtained from
surface tension and conductivity measurements. This was
because it was very difficult to detect the amount of probe
solubilized in the micelles when the CMC value was very
low. This is a common feature for nonionic surfactants with
very low CMC [37].
It was seen that the CMC values of p-NMA obtained
from three different methods were consistent with each
other. The CMC values of nonionic surfactants are gener-
ally lower compared to ionic surfactants. For example, two
kinds of polysorbate surfactants, Tween 20 and Tween 80,
have CMC values of 0.05 and 0.01 mM, respectively [38].
As compared with other nonionic surfactants, the CMC
value of p-NMA was rather high due to the stronger
interaction of p-NMA having extra hydroxyl and amino
groups with water molecules via H-bonding. Also, the
terminal hydroxyl group of p-NMA could cause an increase
of the CMC value. The micelle formation occurred at
higher concentrations because of the short hydrophobic
chain length.
Solubility of p-NMA
The solubility test of the nonionic p-NMA molecule was
evaluated visually in various organic solvents having dif-
ferent polarities both at room temperature (RT) and 40 °C.
The solubility results of the surfactant molecule are shown
in Table 1 and Fig. 9. The surfactant molecule can be
dissolved easily in a variety of polar solvents such as
methanol, ethanol, acetone, and ethyl acetate due to its own
Table 1 Solubility data for
p-NMA
Solvent
RT
40 °C
Zeta Potential
Water
?
?
?
?
?
–
?
?
?
?
?
–
The zeta potential of p-NMA solutions was measured as a
function of surfactant concentration (Fig. 8). The zeta
potential exhibited a value of nearly zero below 0.003 M.
After that, the zeta potential values increased as the con-
centration increased and finally reached a stable value (ca.
Methanol
Ethanol
Acetone
Ethyl acetate
Chloroform
Diethyl ether
Hexane
-
24 mV) at 0.0374 M. The obtained values all were under
–
–
3
0 mV and showed that the p-NMA solutions have limited
–
–
stability [39]. In addition, the concentration value at the
midpoint of the zeta potential curve was overlapped with
?
soluble, - insoluble
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J Surfact Deterg
Fig. 9 Solubility of p-NMA in
a water, b methanol, c ethanol,
d acetone, e ethyl acetate,
f chloroform, g diethyl ether,
and h hexane
amphiphilic nature. P-NMA showed the lack of solubility
in chloroform, diethyl ether, and hexane, as expected. This
was consistent with the structure of this molecule, which
had a short hydrocarbon tail and was very soluble in water.
respectively. In other words, the acidic and basic hydrol-
ysis of p-NMA increased with increasing temperature, and
p-NMA was found to be more resistant against basic
hydrolysis.
Furthermore, the cloud point is a significant factor when
the non-ionic surfactants are used in emulsion polymer-
ization. The value of this point must be at polymerization
temperature or higher. If this condition cannot be obtained
when the non-ionic surfactants are used alone, they must be
used along with ionic surfactants in emulsion polymeriza-
tions [19]. Accordingly, it can be clearly said that p-NMA
with a higher cloud point can be used alone in these
reactions as the emulsion polymerization temperature is
about 80 °C.
Stability to Hydrolysis
The hydrolysis stability of p-NMA was measured against
basic (0.1 N NaOH) and acidic (0.1 N HCl) media at two
different temperatures, 40 and 80 °C. While the p-NMA
solution showed the resistance to hydrolysis with both
basic and acidic treatment at 40 °C, it became cloudy due
to the hydrolysis in both cases at 80 °C (Fig. 10). At this
temperature, the hydrolysis stability of p-NMA was found
to be 180 and 55 min in the basic and acidic media,
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Yasemin Tamer received her Ph.D. degree majoring in Polymer
Chemistry at Yıldız Technical University, Turkey. She is a research
assistant at the Department of Polymer Engineering, Yalova Univer-
sity, Turkey. Her research deals with the synthesis, characterization,
and applications of polymer materials.
2
7:547–553
2
3. Krishnan S, Klein A, El-Aasser MS, Sudol D (2003) Influence of
chain transfer agent on the crosslinking of poly(N-butyl
methacrylate-co-N-methylol acrylamide) latex particles and
films. Macromolecules 36:3511–3518
4. Chen L, Hu T, Yu H, Chen S, Pojman JA (2007) First solvent-
free synthesis of poly(N-methylolacrylamide) via frontal free-
Hale Berber Yamak is a Assistant Professor at the Department of
Metallurgical and Materials Engineering, Yıldız Technical Univer-
sity, Turkey. She received her Ph.D. degree from the Department of
Polymer Chemistry, Yıldız Technical University. Her scientific
studies are on polymer synthesis and characterization, colloidal
polymers, polymer composites, and nano-composites.
2
radical polymerization.
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Polym Sci
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Polystyrene/poly(butyl acrylate) dispersions having N-methylol
groups a spectroscopic study. Macromol Symp 179:305–314
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water-based coatings prepared in the presence of oligomeric and
conventional protective colloids. Prog Org Coat 71:225–233
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surfactant having N,N-dialkylamide, carboxyl, and carboxylate
groups in aqueous NaCl solutions. J Surf Deterg 7:47–52
H u¨ seyin Yıldırım is a professor at the Department of Chemistry,
Yıldız Technical University. He received his Ph.D. degree from
Istanbul Technical University, Turkey. He is also an instructor and the
head of the Department of Polymer Engineering and Science, Yalova
University. His research fields are polymer materials and their
characterizations, polymer coatings, and plastics and rubber
technologies.
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